EP0789410B1 - Batteries et procédé de fabrication d'une matière active positive - Google Patents

Batteries et procédé de fabrication d'une matière active positive Download PDF

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Publication number
EP0789410B1
EP0789410B1 EP97300663A EP97300663A EP0789410B1 EP 0789410 B1 EP0789410 B1 EP 0789410B1 EP 97300663 A EP97300663 A EP 97300663A EP 97300663 A EP97300663 A EP 97300663A EP 0789410 B1 EP0789410 B1 EP 0789410B1
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Prior art keywords
manganese
active material
positive active
surface modification
powder
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German (de)
English (en)
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EP0789410A1 (fr
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Jun Nunome
Takuya Nakashima
Hiroshi Yoshizawa
Seiji Tao
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP01728096A external-priority patent/JP3521597B2/ja
Priority claimed from JP01727996A external-priority patent/JP3353588B2/ja
Priority claimed from JP8047177A external-priority patent/JPH09245785A/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0789410A1 publication Critical patent/EP0789410A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the present invention relates to alkaline-manganese batteries or lithium-ion secondary batteries using the powder of manganese oxides consisting of manganese dioxide or double oxide of manganese and lithium on which a surface modification layer is formed as a positive active material, and a manufacturing method of said positive active materiel for the batteries made-of manganese oxide powder on which a surface modification layer is formed.
  • Various primary batteries employing manganese dioxide as the positive active material such as the carbon-zinc dry batteries called Leclanche type or zinc chloride type batteries employing neutral salts of ammonium chloride or zinc chloride as electrolyte, alkaline manganese batteries employing potassium hydroxide as the electrolyte, and Li/MnO 2 system primary batteries belonging to organic electrolyte lithium batteries employing manganese dioxide as the positive active material have been known well.
  • lithium-ion secondary batteries which can be high-energy density small size rechargeable batteries in next generation have been known also.
  • These batteries employ positive and negative electrodes made of a host material repeating intercalation and deintercalation of lithium-ions by charging and discharging realizing the heavy load discharge, rapid charge, long cyclic life, etc.
  • a double oxide consisting of cobalt and lithium, or LiCoO 2 is used as the positive electrode, while carbon is generally used as the negative electrode.
  • LiMnO 2 or LiMn 2 O 4 which is a double oxide of manganese and lithium.
  • the polarization lowering of the operation voltage of discharging cell could be attributed for three reasons including the resistance polarization due to the electrical ohmic resistance produced in the outer and inner cell, the activation polarization due -to the charge transfer reaction, and the concentration polarization due to the diffusion control process of reaction substance or products.
  • EMD electrolytic manganese dioxide
  • Such a cell has low cycle deterioration even upon reported change/discharge cycles
  • the present invention provides a battery employing as a positive active material manganese oxides consisting of a manganese dioxide or a double oxide of manganese and lithium on which a surface modification layer is formed by deposition of a compound consisting mainly of oxide of at least one element selected from a group of titanium, cobalt, nickel, strontium, and lanthanum as the positive active material.
  • the present invention further provides a manufacturing method of positive active material for a battery by which a surface modification layer is formed by depositing a compound consisting mainly of an oxide of at least one element selected out of a group of titanium, cobalt, nickel, strontium, and lanthanum by dispersing a manganese oxide powder consisting of a manganese dioxide or a double oxide of manganese and lithium in a treatment solution of salt of at least one element selected out of a group of titanium, cobalt, nickel, strontium and lanthanum.
  • MnO 2 powder or highly active EMD powder is used as the positive active material of alkaline manganese batteries in most of the cases. Since the electronic conductivity of EMD powder is not necessarily be very high, a conductive agent consisted mainly of graphite having no direct contribution to its conductivity had to be added up to an amount of 10 wt%.
  • the main discharge reaction of MnO 2 acting as the positive active material in the alkaline electrolyte can be expressed by a uniform solid-phase reaction shown in Eq. (1), wherein not only the improvement of conductivity of active material but the employment of the material minimizing the concentration polarization due to the ion diffusion within the solid phase are desirable.
  • E Eo - RT F ln [Mn 3+ ]solid [Mn 4+ ]solid - RT F ln[OH - ]
  • the present invention is to offer batteries having excellent continuous discharge characteristics realized before even when a heavy load is applied, by employing manganese oxide consisting of EMD powder of which surface is suitably modified as the positive active material having a very little ohmic loss due to the electric resistance and having a small concentration polarization particularly.
  • batteries employing a positive active material consisting of manganese oxide powder having a surface modified by depositing a layer of compound consisting mainly of oxide of at least one element selected out of a group of titanium (Ti), cobalt (Co), nickel (Ni), strontium (Sr), and lanthanum (La) thereon.
  • a positive active material consisting of manganese oxide powder having a surface modified by depositing a layer of compound consisting mainly of oxide of at least one element selected out of a group of titanium (Ti), cobalt (Co), nickel (Ni), strontium (Sr), and lanthanum (La) thereon.
  • Fig. 1 shows a flow-chart of manufacturing process of the invented positive active material consisting of manganese oxide having a surface modified layer.
  • Fig. 2 shows examples of comparative transition curves of single electrode potentials of positive active materials made of surface modified by present invention and conventional untreated EMD powder placed in an alkaline electrolyte.
  • Fig. 3 shows a relationship between the amount of titanium contained in the invented EMD powder of which surface is modified, the electric conductivity, and the gravimetric capacity density thereof.
  • Fig. 4 shows a half vertical cross-section of LR6(AA) size alkaline manganese battery which is a typical example of the invented battery.
  • Fig. 5 are drawings comparing the discharge characteristics of alkaline manganese batteries employing invented positive active material having a surface layer modified by nickel compound with the one obtained by employing conventional positive active material made of untreated EMD powder.
  • Fig. 6 shows a relationship between the total amount of Co and/or Ni contained in the modified surface layer of EMD powder and the discharge capacity ratio.
  • Fig. 7 shows a discharge characteristics of alkaline manganese battery employing invented positive active material having a surface layer modified by La compound, compared with the one obtained by employing a positive active material using conventional untreated EMD powder.
  • Fig. 8 shows a relationship between the total amount of Sr and/or La contained in the surface modified layer of EMD powder and the possible number of pulse discharges.
  • Fig. 9 shows a cross-sectional view of coin type lithium ion secondary cell which is an other typical example of the invented battery.
  • Fig. 10 shows a cross-sectional view of R20(D) size zinc chloride type carbon-zinc dry cell which is an other typical example of the invented battery.
  • the EMD block electrodeposited on a Ti anode held in a high-temperature manganese sulphate bath kept at a temperature of more than 90°C is peeled off first from the Ti anode. After coarsely crashing and washing the blocks of EMD, this is pulverized by a roller-mill obtaining EMD powder having an average grain diameter of 50 ⁇ m, and this is dried by a conventional method before obtaining EMD powder.
  • the surface of EMD powder is subjected to a modification treatment according to the flow-chart of manufacturing process shown in Fig. 1.
  • the surface modification shown in the processes of (1) - (3) may be replaced by processes of coarse crushing of EMD grain, (4) Washing, (5) Neutralization, and a process of Pulverizing. Furthermore, stabilization and improvements of characteristics of modified EMD are possible by applying a heat treatment in a sulfuric acid aqueous solution after Treatment of (2).
  • the ozone (O 3 ) content in the oxidizing agent means direct bubbling of oxygen (O 2 ). including the O 3 generated by the flow-in of O 2 into the ozonizer at a flow rate of 50 ml/min into the treatment solution.
  • the electric conductivity is determined by placing the sample powder of predetermined volume in a die made of PTFE, and by measuring the terminal DC resistance at a state where a pressure of 3t/cm 2 is applied.
  • the moisture is determined by reducing the weight of sample heated and dehydrated at 500°C from the weight of sample dried at 105°C.
  • preparing a working positive electrode by pressing a mixture of sample powder of 10 weight part mixed with acetylene black of 1 weight part on to a platinum (Pt) plate, using a counter electrode made of Pt plate and a reference electrode made of Hg/HgO, and by measuring the capacity of the positive electrode potential reaching to a potential of -300 mV from the reference electrode potential applying a constant current of 10 mA per one gram of the sample in an alkaline electrolyte consisting of 40 wt% potassium hydroxide (KOH) aqueous solution dissolving 3.0 wt% zinc oxide (ZnO), and the capacity ratios of each sample are derived defining the capacity of the EMD powder sample No. 1 as 100.
  • KOH potassium hydroxide
  • ZnO zinc oxide
  • the discharge end potential of -300 mV is employed as a potential corresponding to the discharge ending voltage of alkaline manganese battery which is 0.9 V.
  • Table 1 shows that all of the electric conductivity of Samples Nos. 2 - 7 and Nos. 9 - 10 obtained by treating the EMD powder in a Ti(SO 4 ) 2 aqueous solution are higher by about two orders comparing to that of untreated EMD powder Sample No. 1.
  • tendencies of slightly higher electric conductivity are observed when H 2 SO 4 is added to the treatment solution (Sample Nos. 2 - 7).
  • H 2 SO 4 is added together with the oxidizing agent (Sample Nos. 2, 3, 5, 6, and 7).
  • no particular differences depending on the type of oxidizing agent have been observed.
  • Table 1 proves that not only the electric conductivity improved by two orders but the significantly increased discharge capacity can be obtained without reducing the moisture by using the EMD powder on which a surface modified layer is formed by using a Ti compound,
  • Fig. 2 shows two discharge characteristics of unipolar electrode potential in an alkaline electrolyte obtained with Sample Nos. 1 and 2.
  • Fig. 3 shows also a steady increase of the electric conductivity in proportion to the increase of Ti content in contrast to that of Sample No. 1 which is fixed at 13.7 x 10 -3 S/cm, and shows also a near saturation of electric conductivity at a point exceeding 0.1 wt.%.
  • the gravimetric capacity density is found optimum in a range of titanium content from 0.1 - 5.0 wt.%.
  • Various positive active materials of which surfaces are modified are prepared by adding salts of manganese, nickel, or cobalt to the H 2 SO 4 acidity Ti(SO 4 ) 2 treatment solution according to the case of Embodiment-1, and the electric conductivity, moistures, and the apparent densities thereof are measured. Then, preparing various LR6(AA) type alkaline manganese batteries, the discharge capacity ratios at heavy and medium loads are determined.
  • FIG. 4 A cross-section of experimental LR6 size alkaline manganese battery is shown in Fig. 4 wherein the cap 1A made of nickel plated steel acting its positive terminal is integrally molded, and conductive coating 1B made of carbon paint is coated on the inner wall of the positive can 1.
  • manganese oxide made either of untreated EMD powder or various surface modified EMD powder mixed with graphite at a weight ratio of 9 to 1 is press-molded into a shape of cylinder, and four of the cylinders are inserted into said positive can 1, and positive electrode mold 2 is press- molded on the inner wall of positive can 1.
  • gel negative electrode 4 prepared by dispersing the zinc powder of 2 weight part in a viscose solution of 1 weight part dissolving a gelling agent made of carboxymethyl cellulose (CMC) or polysodium acrylate or others into said alkaline electrolyte is injected.
  • CMC carboxymethyl cellulose
  • negative electrode terminal 6 made of nickel-plated steel on which brass current collector 5 is welded and washer 7 are integrated by plastic sealer 8, and this unit is inserted into gel negative electrode 4.
  • sealer 8 is placed on groove 1C formed by inwardly curling the opening of positive can 1, the upper edge of said can 1 is curled inwardly sealing the can.
  • This cell assembly process is ended by sticking label 9 thereon at the end.
  • Table 1 shows a tabulation of discharge periods where the discharge period obtained by Sample No. 1 cell employing a positive active material made of untreated EMD powder is defined as 100, and the ones of other cells each employing positive active material made of treated EMD powder of which surface layer is modified are defined as the ratios of those to that of Sample No. 1.
  • CMD chemical manganese dioxide
  • Embodiment-3 described before, the improvements of heavy load discharge characteristics of alkaline manganese batteries by employing the EMD powder of which surface is modified by a titanium compound together with a compound of cobalt and/or nickel compound and the cobalt and/or nickel compound including the manganese compound has been explained.
  • LR6 size alkaline manganese batteries utilizing a positive active material formed on the EMD powder of which surface layer is modified are prepared in accordance to Embodiemnt-1 using a solution of cobalt salt and/or nickel salt, or cobalt salt and/or nickel salt including the manganese salt excluding the use of titanium salt in the treatment solution.
  • Fig. 5 shows a higher discharge capacity up to a discharge end voltage of 0.9 V since the discharge voltage is improved by using EMD powder of which surface layer is modified by a nickel compound made- mainly of nickel oxide which could be NiOOH used as the positive electrode.
  • Fig. 6 shows a relationship between the discharge capacity ratio of positive electrode made of EMD powder of which surface is modified by the deposition of Co and/or Ni compound and the total contents of Co and/or Ni. Like the cases of Embodiments-1 and -2, the discharge capacity ratios are determined by conducting single electrode discharge tests in an alkaline electrolyte and defining the one obtained by the untreated EMD powder as 100. Fig. 6 shows also the discharge capacity ratios of every EMD powder of which surface layers are modified by using a Co and/or Ni compound, and these are higher than that (240 mAh/g) of untreated EMD powder. Note is the effectiveness of total contents of Co and/or Ni in a range from 0.1 - 10.0 wt%. in these cases.
  • Electron-microscopic observations made on the surface of EMD powder modified by a Co and/or Ni compound and a Co and/or Ni compound containing a Mn compound has proved the order of surface irregularities less than those observed on the untreated EMD powder. Moreover, like the cases of Embodiments -3 and -4, the higher apparent densities of surface modified EMD powder containing a Mn compound (Sample Nos. 40 - 46 and 48) are observed.
  • Embodiments -1 - -4 have proved the effectiveness of EMD powder of which surfaces are modified by forming a Ti compound or a Co (cobalt) and/or Ni (nickel) compound and by forming a Ti compound containing Mn or Co and/or Ni compound.
  • this Embodiment-5 the effects of the surface modification by using a Sr (strontium) and/or La (lanthanum) compound, and by using a Sr (strontium) and/or La (lanthanum) compound containing Mn compound are confirmed.
  • various LR6-size alkali manganese batteries employing the EMD powder of which surface is modified by a Sr (strontium) and/or La (lanthanum) compound, and by a Sr (strontium) and/or La (lanthanum)compound containing a Mn compound as its positive active material are prepared, and these are subjected to a pulse discharge test.
  • the pulse discharge test is a test simulating a strobe flash for still-camera where the discharge is repeated for a 15 sec., on a constant resistance of 1.8 ohm allowing a rest period of 45 sec., are the number of the discharges is counted until an end voltage of 0.9 V is reached. Defining the number of pulse discharges obtained by the cell of Sample No. 1 employing untreated EMD powder is 100, the ratio of the number of pulse discharges obtained by a cell employing surface modified EMD powder is expressed by the discharge capacity ratio. These results are shown in Tables 6, 7, and 8.
  • Tables 6, 7 and 8 show that all of the discharge capacity ratio obtained with EMD powders on which surface modified layers are formed by a Sr and/or La compound and a Sr and/or La compound containing Mn compound are higher than that obtained with untreated EMD powder (Sample No.1), as improved discharge voltage.
  • Fig. 8 shows a relationship between the pulse discharge cycle counts of LR6-size alkaline manganese batteries employing the EMD powder of which surface is modified by depositing a Sr and La compound as its positive active material and the total contents of Sr and La.
  • Fig. 8 shows also that all of the batteries employing EMD powder of which surface is modified by a Sr and/or La compound show definite improvements of pulse discharge cycle counts, and it is particularly effective when the total content of Sr and/or La is in a range from 0.1 - 10.0 wt%.
  • FIG. 9 A cross-section of coin type cell developed for the evaluation of invented positive electrode is shown in Fig. 9 wherein 21 is a cell-case made of stainless-steel anti-corrosive to the organic electrolyte, 22 is a cell cover made of the same material, 23 is an invented positive electrode, 24 is a current collector for positive electrode 23 made of the same stainless-steel and is spot-welded to the internal surface of cell-case 21, 25 is negative electrode molded graphite powder and pressed against the inside of cell cover 22. 26 is a separator made of porous polypropylene, and 27 is an insulating gasket made of polypropylene.
  • the evaluation cell coin type has a diameter of 20 mm and an overall height of 1.5 mm.
  • the positive active material is prepared by mixing various surface modified EMDs prepared in advance with lithium hydroxide (LiOH) at a ratio forming a double oxide of manganese and lithium, LiMn 2 O 4 of prescribed composition, and this mixture is sintered at a temperature of 860°C for 70 hours in an oxidizing atmosphere.
  • the positive electrode compound is prepared by mixing a conductive agent into polyvinylidenfluoride acting as a binder at a weight part of 5 to 5, and by mixing this mixture into the obtained positive active material at a weight part of 90. Preparing the electrode by molding thus obtained positive electrode compound of a prescribed volume on current collector 24, this is dried at a temperature of 150°C in vacuum condition, and this is assembled into a cell using a negative electrode 25.
  • lithium perchlorate dissolved in a solvent where ethylene carbonate and 1, 3-dimethoxyethane are mixed at an equal volume obtaining a concentration of 1 mol/litter is used. Since positive electrode is deintercalated lithium-ions electrochemically to electrolyte by charging after the cell assembly, and intercalated the lithium ions from electrolyte by discharging, it is obvious that this functions as a positive electrode material for secondary batteries.
  • Table 9 shows the ratio of discharge capacity at a rate of 1.0 mA/cm 2 to that at a rate of 0.2 mA/cm 2 .
  • the surface modified samples show better high-rate discharge characteristics than the one obtained by the referenced sample No.S-1. Moreover, the same effects could be obtained if the surface modification were made on the samples mentioned other than the above.
  • 31 is a positive electrode mix
  • 32 is a carbon rod acting as a positive current collector
  • 33 is a zinc can
  • 34 is a separator
  • 34A is a bottom paper
  • 35 is a plastic sealing cover
  • 35A is a positive terminal plate
  • 36 is a cover paper
  • 36A is sealer
  • 37 is a negative terminal plate
  • 38 is a PVC tube
  • 39 is a metal jacket.
  • Positive electrode mix 31 is prepared by mixing said manganese dioxide with acetylene-black at a weight ratio of 5 : 1, by mixing this into an electrolyte consisting of zinc chloride and ammonium chloride mixed solution, which main constituent is zinc chloride, and by molding.
  • carbon-zinc dry cells show better heavy-load discharge characteristics when a manganese dioxide having a surface modified layer is employed over the cases where the cells employ a manganese dioxide having a unmodified surface layer.
  • an alkaline manganese battery prepared by employing an EMD powder having a surface modified layer by compound consisting mainly of oxide of at least one element selected out of a group of Ti, Co, Ni, Sr, and La, and is used as the positive active material the resistance polarization and the concentration polarization are obviously lowered at the heavy load and continuous discharge so that discharge characteristics of high efficiency can be obtained by the increased discharge voltage and the effective capacity.
  • a Mn compound is introduced in the surface modified layer are found effective also.
  • the effects available with the above-mentioned surface layer modification are not necessarily be limited to the alkali manganese batteries only.
  • a surface modification depositing a compound of at least one element selected out of a group of Ti, Co, Ni, Sr, and La on the surface of not only EMD but CMD and natural manganese dioxide (NMD), and by using this as a positive active material, those can be applied to Leclanche type and zinc chloride type carbon-zinc dry batteries also.
  • the positive active material for the Li/MnO 2 system organic electrolyte lithium primary battery having a high rate discharge characteristics can be obtained.
  • a manganese oxide on which a surface modified layer is formed by depositing a compound of at least one element selected out of a group of Ti, Co, Ni, Sr, and La on the surface of LiMnO 2 or LiMn 2 O 4 powder which is a double oxide of Mn and Li repeating the deintercalation and intercalation of Li by charge and discharge as the positive electrode still-better charge and discharge characteristics can be obtained.
  • the treatment solution of this invention in not necessarily be limitedwithin the usage of sulfates.
  • chlorides or nitrates etc are used as the positive active material of the battery after the treatment, the use of these salt can never be disturbed by the possible introduction of minute anions contained in the treatment solution.
  • chloride solution as the treatment solution acting as the positive active material for carbon-zinc dry batteries wherein NH 4 Cl and/or ZnCl 2 is used as an electrolyte.
  • This invention is to offer batteries using a manganese oxide on which the surface of manganese oxide powder consisting of MnO2, Mn and Li of a double oxide is modified by the deposition of a compound consisting mainly of an oxide of at least one element selected out of a group of Ti, Co, Ni, Sr, and La as its positive active material and a compound made mainly of a Mn oxide by using a solution dissolving a salt of at least one element selected out of a group of Ti, Co, Ni, Sr, and La to which a Mn salt is added.

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  • Battery Electrode And Active Subsutance (AREA)

Claims (12)

  1. Accumulateur utilisant comme matière active positive des oxydes de manganèse constitués d'un dioxyde de manganèse ou d'un oxyde double de manganèse et de lithium sur laquelle est formée une couche de modification de surface par dépôt d'un composé constitué principalement d'oxyde d'au moins un élément choisi parmi le titane, le cobalt, le nickel, le strontium et le lanthane en tant que matière active positive.
  2. Accumulateur selon la revendication 1 utilisant un composé constitué principalement d'oxyde de manganèse dispersé dans ladite couche de modification de surface.
  3. Accumulateur sec au carbone-zinc selon les revendications 1 et 2, utilisant de la poudre de dioxyde de manganèse sur laquelle est formée une couche de modification de surface en tant que matière active positive.
  4. Accumulateur alcalin au manganèse utilisant de la poudre de dioxyde de manganèse sur laquelle est formée une couche de modification de surface en tant que matière active positive selon la revendication 1 ou 2.
  5. Accumulateur alcalin au manganèse utilisant de la poudre de dioxyde de manganèse électrolytique en tant que matière active positive sur laquelle est formée une couche de modification de surface selon les revendications 1 et 2.
  6. Accumulateur primaire au lithium organique utilisant de la poudre de dioxyde de manganèse chauffée et déshydratée en tant que matière active positive après la formation d'une couche de modification de surface selon les revendications 1 et 2.
  7. Accumulateur secondaire aux ions lithium utilisant de la poudre d'un oxyde double de manganèse et de lithium en tant que matière active positive après la formation d'une couche de modification de surface selon la revendication 1 ou 2.
  8. Procédé de fabrication d'une matière active positive pour un accumulateur par lequel est formée une couche de modification de surface par dépôt d'un composé constitué principalement d'un oxyde d'au moins un élément choisi parmi le titane, le cobalt, le nickel, le strontium et le lanthane en dispersant une poudre d'oxyde de manganèse constituée d'un dioxyde de manganèse ou d'un oxyde double de manganèse et de lithium dans une solution de traitement d'un sel d'au moins un élément choisi parmi le titane, le cobalt, le nickel, le strontium et le lanthane.
  9. Procédé de fabrication d'une matière active positive pour des accumulateurs selon la revendication 8, par lequel un composé principalement constitué d'oxyde de manganèse est dispersé dans une couche de modification de surface par l'addition de sel de manganèse dans ladite solution de traitement.
  10. Procédé de fabrication d'une matière active positive pour des accumulateurs selon les revendications 8 et 9, par lequel un sel d'un élément choisi parmi le titane, le manganèse, le cobalt, le nickel, le strontium et le lanthane utilisé pour ladite solution de traitement est d'au moins un type de sel choisi parmi un sulfate, un nitrate et un chlorure.
  11. Procédé de fabrication d'une matière active positive pour des accumulateurs selon les revendications 8, 9 et 10 par lequel la modification de surface est réalisée en ce que ladite solution de traitement est maintenue dans des conditions acides.
  12. Procédé de fabrication d'une matière active positive pour des accumulateurs selon la revendication 8 à la revendication 11 par lequel est formée la couche de modification de surface par addition à la solution de traitement d'au moins un agent oxydant choisi parmi l'air, l'oxygène, l'ozone, le perchlorate de sodium et le persulfate de sodium.
EP97300663A 1996-02-02 1997-01-31 Batteries et procédé de fabrication d'une matière active positive Expired - Lifetime EP0789410B1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP1728096 1996-02-02
JP1727996 1996-02-02
JP01728096A JP3521597B2 (ja) 1996-02-02 1996-02-02 アルカリ乾電池およびアルカリ乾電池用マンガン酸化物の製造法
JP01727996A JP3353588B2 (ja) 1996-02-02 1996-02-02 電池および電池用マンガン酸化物の製造法
JP17280/96 1996-02-02
JP17279/96 1996-02-02
JP8047177A JPH09245785A (ja) 1996-03-05 1996-03-05 電池および電池用マンガン酸化物の製造法
JP47177/96 1996-03-05
JP4717796 1996-03-05

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EP0789410A1 (fr) 1997-08-13
US5928714A (en) 1999-07-27
US5744266A (en) 1998-04-28
DE69701411D1 (de) 2000-04-20

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